The absolute value of the difference in electronegativity (ΔEN) of two bonded atoms provides a rough measure of the polarity to be expected in the bond and, thus, the bond type. When the difference is very small or zero, the bond is covalent and nonpolar. When it is large, the bond is polar covalent or ionic. The absolute values of the electronegativity differences between the atoms in the bonds H–H, H–Cl, and Na–Cl are 0 (nonpolar), 0.9 (polar covalent), and 2.1 (ionic), respectively. The degree to which electrons are shared between atoms varies from completely equal (pure covalent bonding) to not at all (ionic bonding). Figure \(\PageIndex{4}\) shows the relationship between electronegativity difference and bond type. Show
A rough approximation of the electronegativity differences associated with covalent, polar covalent, and ionic bonds is shown in Figure \(\PageIndex{4}\). This table is just a general guide, however, with many exceptions. For example, the H and F atoms in HF have an electronegativity difference of 1.9, and the N and H atoms in NH3 a difference of 0.9, yet both of these compounds form bonds that are considered polar covalent. Likewise, the Na and Cl atoms in NaCl have an electronegativity difference of 2.1, and the Mn and I atoms in MnI2 have a difference of 1.0, yet both of these substances form ionic compounds. The best guide to the covalent or ionic character of a bond is to consider the types of atoms involved and their relative positions in the periodic table. Bonds between two nonmetals are generally covalent; bonding between a metal and a nonmetal is often ionic. Some compounds contain both covalent and ionic bonds. The atoms in polyatomic ions, such as OH–, \(\ce{NO3-}\), and \(\ce{NH4+}\), are held together by polar covalent bonds. However, these polyatomic ions form ionic compounds by combining with ions of opposite charge. For example, potassium nitrate, KNO3, contains the K+ cation and the polyatomic \(\ce{NO3-}\) anion. Thus, bonding in potassium nitrate is ionic, resulting from the electrostatic attraction between the ions K+ and \(\ce{NO3-}\), as well as covalent between the nitrogen and oxygen atoms in \(\ce{NO3-}\).
Example \(\PageIndex{1}\): Electronegativity and Bond Polarity Bond polarities play an important role in determining the structure of proteins. Using the electronegativity values in Table A2, arrange the following covalent bonds—all commonly found in amino acids—in order of increasing polarity. Then designate the positive and negative atoms using the symbols δ+ and δ–: C–H, C–N, C–O, N–H, O–H, S–H Solution The polarity of these bonds increases as the absolute value of the electronegativity difference increases. The atom with the δ– designation is the more electronegative of the two. Table \(\PageIndex{1}\) shows these bonds in order of increasing polarity.
Exercise \(\PageIndex{1}\) Silicones are polymeric compounds containing, among others, the following types of covalent bonds: Si–O, Si–C, C–H, and C–C. Using the electronegativity values in Figure \(\PageIndex{3}\), arrange the bonds in order of increasing polarity and designate the positive and negative atoms using the symbols δ+ and δ–. Answer
This text is published under creative commons licensing, for referencing and adaptation, please click here. 4.1 Introduction to Covalent Molecules and CompoundsHow to Recognize Covalent Bonds4.2 Electron SharingSingle Covalent Bonds Between the Same AtomsSingle Covalent Bonds Between Different AtomsMultiple Covalent BondsCoordinate Covalent Bonds4.3 Electronegativity and Bond Polarity4.4 Properties of Molecular Compounds4.5 Naming Binary Molecular Compounds4.6 Chapter Summary4.7 ReferencesChapter 4 – Covalent Bonds and Molecular CompoundsChemical bonds are generally divided into two fundamentally different types: ionic and covalent. In reality, however, the bonds in most substances are neither purely ionic nor purely covalent, but lie on a spectrum between these extremes. Although purely ionic and purely covalent bonds represent extreme cases that are seldom encountered in any but very simple substances, a brief discussion of these two extremes helps explain why substances with different kinds of chemical bonds have very different properties. Ionic compounds consist of positively and negatively charged ions held together by strong electrostatic forces, whereas covalent compounds generally consist of molecules, which are groups of atoms in which one or more pairs of electrons are shared between bonded atoms. In a covalent bond, atoms are held together by the electrostatic attraction between the positively charged nuclei of the bonded atoms and the negatively charged electrons they share. This chapter will focus on the properties of covalent compounds. 4.1 Introduction to Covalent Molecules and CompoundsJust as an atom is the simplest unit that has the fundamental chemical properties of an element, a molecule is the simplest unit that has the fundamental chemical properties of a covalent compound. Thus, the term molecular compound is used to describe elements that are covalently bonded and to distinguish the compounds from ionic compounds. Some pure elements exist as covalent molecules. Hydrogen, nitrogen, oxygen, and the halogens occur naturally as the diatomic (“two atoms”) molecules H2, N2, O2, F2, Cl2, Br2, and I2 (part (a) in Figure 4.1). Similarly, a few pure elements exist as polyatomic (“many atoms”) molecules, such as elemental phosphorus and sulfur, which occur as P4 and S8 (part (b) in Figure 4.1). Figure 4.1 Elements That Exist as Covalent Molecules. (a) Several elements naturally exist as diatomic molecules, in which two atoms (E) are joined by one or more covalent bonds to form a molecule with the general formula E2. (b) A few elements naturally exist as polyatomic molecules, which contain more than two atoms. For example, phosphorus exists as P4 tetrahedra—regular polyhedra with four triangular sides—with a phosphorus atom at each vertex. Elemental sulfur consists of a puckered ring of eight sulfur atoms connected by single bonds. Selenium is not shown due to the complexity of its structure. Each covalent compound is represented by a molecular formula, which gives the atomic symbol for each component element, in a prescribed order, accompanied by a subscript indicating the number of atoms of that element in the molecule. The subscript is written only if the number of atoms is greater than 1. For example, water, with two hydrogen atoms and one oxygen atom per molecule, is written as H2O. Similarly, carbon dioxide, which contains one carbon atom and two oxygen atoms in each molecule, is written as CO2. Covalent compounds that predominantly contain carbon and hydrogen are called organic compounds. The convention for representing the formulas of organic compounds is to write carbon first, followed by hydrogen and then any other elements in alphabetical order (e.g., CH4O is methyl alcohol, a fuel). Compounds that consist primarily of elements other than carbon and hydrogen are called inorganic compounds; they include both covalent and ionic compounds. The convention for writing inorganic compounds, involves listing the component elements beginning with the one farthest to the left in the periodic table, as in CO2 or SF6. Those in the same group are listed beginning with the lower element and working up, as in ClF. By convention, however, when an inorganic compound contains both hydrogen and an element from groups 13–15, hydrogen is usually listed last in the formula. Examples are ammonia (NH3) and silane (SiH4). Compounds such as water, whose compositions were established long before this convention was adopted, are always written with hydrogen first: Water is always written as H2O, not OH2. Typically this distinguishes when hydrogen is participating in a covalent bond rather than an ionic interaction, as seen in many of the inorganic acids, such as hydrochloric acid (HCl) and sulfuric acid (H2SO4), as described in chapter 3. How to Recognize Covalent BondsIn Chapter 3, we saw that ionic compounds are composed predominantly of a metal + a nonmetal. Covalent molecules, on the otherhand, are typically composed of two nonmetals or a nonmetal and a metalloid. This is an initial screening method that you can use to categorize compounds into the ionic or the covalent cagetogy. Figure 4.2 Recognizing Ionic vs Covalent Compounds. Typically compounds that are formed from a combination of a metal with a nonmetal have more ionic bond character whereas compounds formed from two nonmetals or a metalloid and a nonmetal show more covalent character. Although compounds usually lie on a spectrum somewhere between fully ionic and fully covalent character, for naming purposes, this guideline works well. 4.2 Electron SharingSingle Covalent Bonds Between the Same Atoms
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